Di(omega-hydroxyalkyl) methylcyclopentanes



United States Patent ABSTRACT OF THE DISCLOSURE This invention relatesto the production of di(whydroxyalkyl)methylcyclopentane of the formula:

Hz\Ha HOCH2(CH2CH2)y"- --(CHZCH2)ZCHZOH H CH wherein y and z designateintegers of from 0 to 8, by reacting 1,3-butadiene with anisoalkylaluminum, optionally growing the resulting polymer Withethylene, oxidizing the polymer, and then hydrolyzing the oxygenatedpolymer.

This application is a division of application Ser. No. 247,838,entitled, Dialiphatic-Substituted Methylcyclopentanes, filed Dec. 28,1962 now Patent No. 3,356,704.

The present invention is concerned with a novel process for theproduction of dialiphatic-substituted methylcyclopentanes, includingpolymeric organoaluminum compounds, utilizing 1,3-butadiene and anisoalkylaluminum as initial reactants. The invention is also concernedwith certain of the dialiphatic-substituted methylcyclopentanes,particularly, the polymeric organoaluminum compounds and the highermolecular weight dienes, monoand diepoxides, and diols hereinbelowdescribed, as novel and useful compositions of matter.

In accordance with this invention, 1,3-butadiene is initially reactedwith an isoalkylaluminum to form a novel polymer composed of asubstantial proportion of recurring di(aluminomethyl)methylcyclopentaneunits, viz. up to about 35 percent or slightly more of such units basedupon the total number of recurring units in the polymer. This reaction,in which two moles of 1,3- butadiene concurrently (i.e. in oneprocedural step) cyclize and displace an isoalkyl radical on each of twomoles of the isoalkylaluminum to form a polymer composed of recurringdi(aluminomethyl)methylcyclopentane units can be represented by thepartial equation:

wherein each R, independently, designates an alkyl radical, preferablycontaining from 1 to 4 carbon atoms.

It is to be noted that, as herein employed, the symbol a1 designatesone-third of an atom of aluminum. Thus, in all instances, each aluminumatom is attached to three other atoms. It is also to be noted that therecurring di- (aluminomethyl)methylcyclopentane units of the polymer maycomprise an isomeric mixture of 1,2-di(a1uminomethyl) 3methylcyclopentane and 1,3 di(aluminomethyl)-2-methylcyclopentane units,the latter generally "ice predominating in the polymer. In addition, thepolymer also contains recurring linear or branched-chain dialuminoalkaneunits, as well as various terminal units.

It was unexpected that a polymer comprised of a substantial proportionof recurring di(aluminomethyl)- methylcyclopentane units could beobtained by the reaction of 1,3-butadiene and an isoalkylaluminum in oneprocedural step, since such reactants have heretofore been known toproduce only an acyclic dialuminoalkane polymer via a plurality ofprocedural steps. Moreover, through subsequent reaction of thedi(aluminomethyl)- methylcyclopentane-containing polymer as hereinafterdescribed, a novel route to various dialiphatic-substitutcdmethylcyclopentanes has now been provided.

Several process conditions have been found to be of importance to theproduction of the di(aluminomethyl)- methylcyclopentane-containingpolymer in accordance with this invention. First of all, 1,3-butadienemust be brought into contact and admixed with an excess over thestoichiometric amount of isoalkylaluminum required for the reaction soas to assure a substantial degree of cyclization and the production ofthe polymer in one procedural step. In addition, for similar reasons,the amount of isoalkylaluminum employed must be sufficient to providesuch excess in the reaction zone at all times during the reaction. Thus,an excess over one-third of a mole of isoalkylaluminum, and preferablyat least about one mole of isoalkylaluminum, per mole of 1,3-butadieneis employed and maintained in the reaction zone during the reaction. Inpractice, for instance, gaseous 1,3-butadiene can be bubbled slowlythrough excess liquid isoalkylaluminum. Alternatively, the reaction canbe carried out continuously in a tubular reactor if a several foldexcess of isoalkylaluminum is employed.

It has also been found expedient, during the course of the reaction, toremove the isoolefin formed as a byproduct. At the same time, it ispreferable to remove unreacted 1,3-butadiene. Concor'dant therewith, thereaction can be carried out in an open system under atmospheric pressureor in a closed system under autogeneous pressure providing the system isequipped, in the latter instance, with means for venting or removingby-product isoolefin, and preferbaly unreacted 1,3-butadiene, during thecourse of the reaction. The removal of by-product isoolefin in thismanner serves to drive the reaction to completion and minimizes oreliminates side reactions between the isoolefin and the growing polymer.At the same time, by the removal of unreacted 1,3-butadiene, theessential presence of excess isoalkylaluminum in the reaction zone isassured, and the possible formation of a thermal dimer of 1,3-butadienewhich would contaminate the desired polymer is obviated.

The isoalkylaluminums which can be reacted with 1,3- butadiene ascontemplated by this invention are the triisoalkylaluminums anddiisoalkylaluminum hydrides represented by the formulae:

H /R /R Al CHzCH and HA1 CH2CE R 3 R a wherein R is as defined above.The size of the isoalkyl radical is limited only in that thecorresponding isoolefin formed as a by-product must be readily removablefrom the reaction mixture during the course of the reaction, preferablyas a gas. Suitable isoalkylaluminums include, by way of illustration,triisobutylaluminum, tri-Z-methylbutylaluminu-m, tri 2ethylhexylaluminum, diisobutylaluminum hydride, di-2-methylbutylaluminumhydride, di-Z-ethylhexylaluminum hydride, and the like. The preferredisoalkylaluminum is triisobutylaluminum. Isoalkylaluminum containing twoor three different isoalkyl radi- -hals can also be employed as areactant.

An inert organic solvent can also be incorporated in the reactionmixture, if desired. Suitable solvents include, for instance, heptane,octane, decane, benzene, toluene, Xylene, decalin, and the like.

The reaction temperature can vary broadly in the range of from about 80C. to about 150 C., substantially lower temperatures engendering anexcessively slow rate of reaction, While at higher temperatures,undesirable side reactions may occur. Preferably, a reaction temperatureof from about 90 C. to about 130 C. is employed. At such temperatures,the reaction is generally carried out for a period of from about 5 toabout 50 hours. However, longer or shorter reaction periods sufficientto produce the desired polymer can also be employed.

The polymer thus obtained is ordinarily solid at room temperature,changing to a viscous liquid at elevated temperatures, and can beseparated from excess isoalkylaluminum and any solvent present in anyconvenient manner. For instance, the polymer can be recovered as theresidue product obtained upon removal of the more volatile components ofthe reaction mixture by distillation or evaporation, etc.

In another aspect of this invention, when a polymer containing recurringdi(aluminoalkyl)methylcyclopentane units of higher molecular weight,i.e. of increased aluminoalkyl chain length, is desired, the polymer,obtained as described above, is subsequently subjected to a growthprocess by reaction with ethylene in the absense of a catalyst, andpreferably under pressure. This reaction, in which a novel polymercomposed of a substantially equal proportion of recurringdi(aluminoalkyl)methylcyclopentane units as compared with that of itspolymeric precursor is produced, can be represented by the partialequation:

H 2 H CH3 H wherein y and z designate integers of from zero to apositive value, at least one of which must be a positive value as aconsequence of the reaction with ethylene; the sum of y plus 2 beingequal to x, the number of moles of ethylene added per recurring unit ofthe polymer. Thus, in the growth process, ethylene units are insertedbetween aluminum atoms and adjacent carbon atoms. A similar growthprocess also occurs in other recurring units present in the polymer, aswell as in terminal units. In addition, the grown" polymer will containa minor amount of units which have not reacted with ethylene.

The amount of ethylene reacted should be sufiicient to effect the growthof the recurring units of the polymer t0 the extent desired, asdetermined, for instance, :by the subsequent use of the grown polymer.Useful polymers, by way of illustration, are those in which theaminoalkyl chain length of the recurringdi(aluminoalkyl)methylcyclopentane units have grown by a statisticallyvarying length of from 2, and preferably from about 6 to about 32 carbonatoms, i.e. wherein y and z in each recurring unit designate integershaving a value of from zero to about 8, at least one of which has apositive value, the sum which is preferably a value of at least 3. Tothis end, the polymer for whic growth is desired is reacted withethylene in a proportion of at least 1.5

moles, and preferably from about 4.5 moles, to about 24 moles ofethylene per atom of aluminum present in the polymer or per mole ofisoalkylaluminum initially reacted to produce the polymer. In practice,however, an excess over the required amount of ethylene is generallycharged. If desired, an inert organic solvent such as those describedabove in connection with the initial polymer formation can also beincorporated in the reaction mixture.

The reaction temperature for the growth process can vary broadly in therange of from about C. to about 190 C., substantially lower temperaturesengendering an excessively slow rate of reaction, while at highertemperatures, undesirable side reactions may occur. Preferably, areaction temperature of from about C. to about C. is employed,particularly in connection with a batch operation. At such temperatures,the reaction is generally carried out for a period of from about 5 toabout 50 hours. However, longer or shorter reaction periods consistentwith the production of the grown polymer can also be employed. Thus, forinstance, the reaction can also be carried out continuously in a tubularreactor at a temperature preferably of from about 120 C. to about C. forvery short contact periods. The amount of ethylene entering the polymercan be controlled in part by the control of temperature, reactionperiod, etc, and is readily determinable by one skilled in the art inlight of this disclosure.

After the desired amount of ethylene has been incorporated in thepolymer, as determined, for instance, by the moles of ethylene consumed,the system is vented so as to remove any excess ethylene. The grownpolymer thus obtained, like its polymeric precursor, is ordinarily solidat room temperature, changing to a viscous liquid at elevatedtemperatures, and can be separated from any solvent present in anyconvenient manner, as, for instance, by the techniques described abovein connection with the recovery of the ungrown polymer.

In still another aspect of this invention, the polymeric productshereinabove described are subjected to a displacement process bysubsequent reaction with ethylene in the presence of a catalyst, andpreferably under pressure, to form a useful class of dienes, viz.di(w-alkenyl) methylcyclopentanes. In one embodiment of this aspect ofthe invention, when using an ungrown polymer, i.e. the polymer obtainedin accordance with Equation I, the catalyzed reaction with ethylene canbe represented by the partial equation:

wherein the double bonds of the methylene radicals are attached tosingle carbon atoms of the cyclopentane nucleus. Similarly, thecatalyzed reaction of ethylene with the grown polymer ibtained inaccordance with Equation III can be represented by the partial equation:

wherein y and z are each positive values within the meaning hereinabovedefined 'by y and z. Alternatively, when the grown polymer is such thaty or z is zero, the catalyzed reaction with ethylene can be representedby the partial equation:

wherein the double bond attached directly to the cyclopentane nucleus isattached to a single carbon atom thereof, and m designates a positiveinteger equal to the positive value of y or z. A similar displacementprocess also occurs in other recurring units present in the polymer aswell as in terminal units.

In the displacement process, the polymer is reacted with ethylene in aproportion of at least 3 mols of ethylene per atom of aluminum presentin the polymer. In practice, however, an excess over the required amountof ethylene is generally charged. If desired, an inert organic solventsuch as those described above in connection with the initial polymerformation can also be incorporated in the reaction mixture. In addition,the presence of a small amount of an acetylenic compound, such asphenylacetylene, has been found to prolong the life of the catalystemployed and to minimize the migration of double bonds in the dieneproduct.

Suitable catalysts for use in the displacement process include nickel,cobalt and platinum. Such metals can be incorporated in the reactionmixture in elemental form or, preferably, as an inorganic or organicsalt such as nickel chloride, platinum chloride, cobalt chloride, nickelacetylacetonate, platium acetylacetonate, cobalt acetylacetonate, andthe like. The use of such salts ordinarily engenders a better dispersionof the metal in the reaction mixture. The catalyst is generally employedin a concentration of from about 0.0001 to about 1 percent by Weight ofmetal based upon the weight of the polymer undergoing reaction, althoughhigher or lower catalytic amounts can also be used. Preferably, thecatalyst is employed in a concentration of from about 0.005 to about 0.1percent by weight based in like manner.

The reaction temperature for the displacement proc ess can vary broadlyin the range of from about 25 C. to about 120 C., particularly inconnection with a batch operation. Here again, substantially lowertemperatures engender an excessively slow reaction rate, while at highertemperatures, in the presence of the catalyst, undesirable sidesreactions may occur. The preferred reaction temperature is from about 40C. to about 70 C. At such temperatures the reaction is generally carriedout for a period of from about 1 to about 24 hours. However, longer orshorter reaction periods consistent with diene formation can also beemployed.

The displacement process can also be conducted omitting the use of acatalyst at substantially higher reaction temperatures of from about 250C. to about 350 C., or slightly higher, and preferably from about 280 C.to about 320 C. At such higher temperatures, the reac tion is bestcarried out continuously in a tubular reactor for short contact periods.

The diene product thus obtained is ordinarily liquid in form at roomtemperature, and can be recovered from the reaction mixture in anyconvenient manner. Preferably, upon completion of the displacementprocess, the reaction mixture is hydrolyzed to assist the removal ofalkylaluminum formed as a 'by-product. Hydrolysis can be effected byreaction with water, aqueous alcohol, and/ or dilute acid. Uponhydrolysis, aluminum hydroxide is formed. The diene product can then berecovered by distillation of the organic phase of the reaction mixture.The removal of by-product alkylaluminum in this manner prevents thereversal of the displacement process which might otherwise occur upondistillation of the diene product.

Due to the nature of the polymer employed as precursors, the dieneproduct may comprise an isomeric mixture of1,2-di(w-alkenyl)-3-methylcyc1opentanes and 1,3-di(w-alkenyl)-2-methylcyclopentanes of statistically varying molecularweight (alkenyl chain length), the latter generally predominating in theproduct especially in the 1, trans-2, cis-3 form. In addition,a,w-alkadienes of statistically varying molecular weight are alsoproduced. Such mixture can be resolved into components of narrow carboncontent ranges by fractional distillation and the products analyze-d bygas-chromatography.

Of the dienes produced in accordance with this invention, there can bementioned:

and the like. The higher molecular weight dienes containing from 14 toabout 40 carbon atoms are contemplated as novel compositions of matter.

The dienes can subsequently be polymerized in accordance withconventional processes for the polymerization of olefinicallyunsaturated compounds to produce useful polymers. The dienes can also bereacted in accordance with conventional processes for the epoxidation ofolefinically unsaturated compounds to produce the vicinal monoanddiepoxides represented by the formulas:

VII

wherein R designates a methyleneoxy, i. e.

radical attached to a single carbon atom of the cyclopentane nucleus;

VIII

HWH

7 and wherein R and m are as defined above; and

CH3 H(c) wherein y and z are as defined above. The specific structure ofthe epoxide product will depend upon the diene employed as a precursor.For instance, the epoxides represented by Formulas VII(a) and (b) arederived from the dienes obtained in accordance with Equation IV; theepoxides represented by Formulas VIII(a) and (b) are derived from thedienes obtained in accordance with Equation VI; and the epoxidesrepresented by formulas IX(a) to (c) are derived from the dienesobtained in accordance with Equation V. The formation of a monoordiepoxide will depend for the most part upon the amount of epoxidizingagent employed, and is readily determinable by one skilled in the art inlight of this disclosure. It is to be noted that the reaction of thediene obtained in accordance with Equation VI with an amount ofepoxidizing agent sufficient to produce a monoepoxide will generallyresult in the selective epoxidation of the bare methylene radicalattached to the cyclopentane nucleus rather than the higher w-alkenylradical. On the other hand, the reaction of the diene obtained in accordance with Equation V with an amount of epoxidizing agent sufficient toproduce a monoepoxide may result in the production of an isomericmixture of the cpoxides represented by the Formulas IX(a) and (b).Mixtures of monoand diepoxides may also be produced depending, forinstance, upon the amount of epoxidizing agent empoyed.

The epoxidation of the dienes can be carried out by reaction withperacetic acid or other conventional epoxidizing agent, in a suitablesolvent such as ethyl acetate, if desired, and at a temperature whichcan vary broadly in the range of from about 25 to about 150 C.Preferably, reaction temperatures of from about C. to about 90 C. areemployed. At such temperatures, a reaction period of from about 1 toabout 10 hours is usually sufficient for a complete reaction. However,longer or shorter reaction periods consistent with epoxide formation canalso be employed.

The epoxide product can then be recovered from the raction mixture inany convenient manner. For instance, the epoxide product can berecovered as the residue obtained upon removal of the more volatilecomponents of the reaction mixture by distillation or evaporation andresolved, if desired, by further distillation when more than one epoxideis produced.

As typical of the epoxides produced in accordance with this invention,there can be mentioned:

1-methyleneoxy-3-methylene-2-methylcyclopentane,

1,3 -dimethy1eneoxy-2-methylcyclopentane,

1 ,2-dimethyleneoXy-3-methylcyclopentane,

1-methyleneoxy-3- 4-pentenyl -2-methylcyclopentane,

1-methyleneoxy-3- (4,5-epoxypentyl)-2- methylcyclopentane,

1-methyleneoxy-3-(6-heptenyl) -2-methylcyclopentane,

1-methyleneoxy-3- 6,7-epoxyheptyl -2- mcthylcyclopentane,

1-methyleneoxy-3- 8-n0nenyl) -2-methylcyclopentane,

1-methyleneoxy-3 8 ,9-epoxynonyl -2- methylcyclopentane,

l-methyleneoxy-Z- 8,9-epoxynonyl -3- methylcyclopentane,

1-(2propeny1) -3- (2,3 -epoxypropyl -2- methylcyclopentane,

1,3-di (2,3 -epoxypropyl) -2-methylcyclo pentane,

1,2-di 2,3-epoxypropyl -2-methylcyclopentane 1- 2-p ropenyl -3-4,5-epoxypentyl -2- methylcyclopentane,

1- 2, 3-epoxypropyl) -3 (4-pentenyl -2- methylcyclopentane,

1- (2,3 -epoxypropyl -3- (4,5epoxypentyl -2- methylcyclopentane,

1- Z-propenyl -3 8,9-epoxynonyl -2- methylcyclopentane,

l- (2, 3-epoxypropyl -3- 8-nonenyl -2- methylcyclopentane,

1- (2-propenyl -3 8,9-epoxynonyl -2- methylcyclopentane,

1- (2,3 -epoxypropyl -3- 8,9-epoxynonyl -2- methylcyclopentane,

l- G-heptenyl) 3-3 (6,7-epoxyheptyl -2- methylcyclopentane,

1,3-di 6,7 -epoxyheptyl) -2-methylcyclopentane,

1- 4,5-epoxypentyl -3-( l 6, l7-epoxyheptadecyl -2- methylcyclopentane,and the like.

The higher molecular weight epoxides, and particularly the diepoxides,containing from 14 to about 40 carbon atoms are contemplated as novelcompositions of matter.

The epoxides produced in accordance with this invention can behomopolymerized or reacted with organic hardeners such as polycarboxylicacids or anhydrides, polyamines, or polyols to produce curable resinshaving a wide variety of uses, particularly as molded articles. Theresins thus obtained from the novel epoxides of this invention, andparticularly the diepoxides, may be characterized by enhanced impactstrength and thermal shock resistance. The novel diepoxides of thisinvention are also suited for use as plasticizers for vinyl resins. Thenovel monoepoxides of this invention, on the other hand, can becopolymerized with conventional vinyl monomers to produce resins havingenhanced heat and/ or light stability.

In a further aspect of this invention, the polymers obtained inaccordance with Equations I and III are converted to novel and usefuldiols, viz. di(w-hydroxyalkyl)methylcyclopentanes represented by theformula:

wherein y" and z" independently designate integers of from O to 8. Thespecific structure of the diols will depend upon the polymer employed asa precursor. Thus, the diols represented by Formula X wherein y" and 1"each designate zero are derived from the polymer obtained as describedabove in accordance with Equation I; while the diols represented byFormula X wherein y" and/ or z" designate a positive integer are derivedfrom the grown) polymer obtained as described above in connection withEquation III, with y" and 2" being equal to y and z, respectively.

The conversion of the polymer to a diol can be carried out by contactingthe polymer at a temperature maintained in the range from about 0 C. toabout C., and preferably from about 30 C. to about 60 C., with oxygen soas to insert an oxygen atom between each aluminum atom of the polymerand the adjacent carbon atom. Such contact can be efiected, forinstance, by

passing dry air or a nitrogen-oxygen mixture into a reaction mixturecontaining the polymer. Since the reaction is exothermic, it isdesirable in some instances to use a low concentration of oxygen at thebeginning of the reaction and thereafter increase the oxygenconcentration in the reactant gas stream as the rate of reactiondecreases. Near the end of the reaction, pure oxygen can be used toinsure completion. If desired, an inert organic solvent such as thosedescribed above in connection with the initial polymer formation canalso be incorporated in the reaction mixture.

After the oxygenation step, water or dilute acid is added to thereaction mixture to convert the oxygenated polymer to the diol. Water ispreferred, as it readily hydrolyzes the polymer, forming the diol andaluminum hydroxide as a byproduct. Alternatively, the oxygenated polymercan be hydrolyzed to produce the desired diol by reaction with aqueousalcohol.

The diols thus obtained can be recovered from the reaction mixture inany convenient manner, as, for instance, by distillation of the organicphase of the reaction mixture, etc. Moreover, due to the nature of thepolymers employed as precursors, the diol product may comprise anisomeric mixture of 1,2-di(w-hydroxyalkyl)-3-methylcyclopentanes and1,3-di(w-hydroxyalkyl)-2-methylcyclopentanes of statistically varyingmolecular weight (hydroxyalkyl chain length), the latter generallypredominating in the product especially in the 1, trans-2, cis-3 form.In addition, a,w-alkanediols of varying molecular weight are alsoproduced. Such mixture can be resolved into components of narrow carboncontent ranges by fractional distillation and the products analyzed bygas chromatography. As typical of the diols produced in accordance withthis invention, there can be mentioned:

1,3-di (hydroxymethyl -2-methylcyclopentane,

1,2-di(hydroxymethyl)-3-methylcyclopentane,

1-hydroxymethyl-3-(3-hydroxypropyl) 2 methylcylopentane,

1-hydroxymethyl-3- (S-hydroxypentyl -2-methylcyclopentane,

1-hydroxymethyl-3-(7-hydroxyheptyl) 2 methylcyclopentane,

1-hydroxymethyl-3-(9-hydroxynonyl -2 methylcyclopentane,

1-hydroxymethyl-2-(9-hydroxynonyl)-3 methylcylopentane,

The higher molecular weight diols, containing from 14 to about 40 carbonatoms are contemplated as novel compositions of matter.

The diols produced in accordance with this invention can be employed asorganic hardeners by reaction with epoxides, such as3,4-epoxy-6-methylcyclohexylmethyl3,4-epoxy-6-methylcyclohexanecarboxylate and the like, in conventionalmanner to produce curable resins having a wide variety of uses,particularly as molded articles. The resins thus produced from the noveldiols of this invention may be characterized by enhanced impact strengthand thermal shock resistance.

The polymers obtained in accordance with Equations I and HI can also behydrolyzed by reaction with aqueous alcohol and/or dilute acid to formtrialkylcyclopentanes represented by the formula:

wherein y" and z" are as defined above. The trialkylcyclopentanes thusproduced can be recovered from the reaction mixture in any convenientmanner, as, for instance, by distillation of the organic phase of thereaction mixture, etc. Moreover, due to the nature of the polymersemployed as precursors, the hydrolyzed product may comprise an isomericmixture of 1,2,3-trialkylcyclopentanes of statistically varyingmolecular weight (alkyl chain length). In addition, linear orbranched-chain alkanes of statistically varying molecular Weight arealso produced. Such mixture can be resolved into components of narrowcarbon content range by fractional distillation and the productsanalyzed by gas chromatography. The trialkylcyclopentanes can also beobtained by the reaction with hydrogen of thedi(w-alkenyl)methylcyclopentanes represented above by Formulas VI toVII'I in accordance with conventional processes for the hydrogenation ofolefinically unsaturated compounds.

The invention, in its various aspects, can be illustrated further by thefollowing examples:

Example I In a one-liter flask equipped with a stirrer, condenser,thermometer, inlet tube, and attachment to wetand dryice traps, gaseous1,3-butadiene was slowly bubbled through 160 grams of liquidtriisobutylaluminum over a period of 28 hours at a temperaturemaintained in the range of from 110 C. to 120 C. During the course ofthe ensuing reaction, 126 grams of isobutylene, formed as a by-prdouct,and 410 grams of unreacted 1,3-butadiene which had bubbled through theliquid triisobutylaluminum were removed. A polymer comprised of asubstantial proportion of recurring di(aluminomethyl)rnethylcyclopentaneunits was formed and found to be a viscous liquid at a temperature of110 C. and a colorless solid at room temperature. The polymer washydrolyzed by reaction with 300 milliliters of ethanol at a temperatureof C. Upon hydrolysis 20.2 grams of butane, 10.3 grams of isobutane, 2.3grams of isobutylene, and 1 gram of butadiene were evolved and removed.Hydrolysis was thereafter continued by reaction with dilute hydrochloricacid at a temperature of 50 C. A two-phase reaction mixture comprisingan upper oragnic layer and a lower aqueous layer was formed. The organiclayer was separated, washed with water, dried over magnesium sulfate andfiltered, thereby yielding 55 grams of mixed hydrocarbons. A 44-gramportion of this mixture was distilled to yield the following fractions:

Fraction Weight, B.P. C.) an d grams 29 -120 1. 413 0. 757 3 /atm.70/50mm. Hg 1. 426 0. 775 70/50 mm. Hg.118/50 mm. Hg. 1. 443 0.813 1. 4540.833

8 118/50 mm. Hg.82/0.3 mm.

Residue. 2

C as Well as C and C hydrocarbons were also found to be produced.

1 1 EXample II In a manner similar to that described above in Example I,1,3-butadiene was reacted with triisobutylaluminum to produce 612 gramsof a polymer comprised of a substantial proportion of recurringdi(aluminomethyl)methylcyclopentane units. A mixture of 215 grams ofthis polymer, 350 grams of benzene, 0.3 ml. of phenylacetylene, and 0.1ml. of nickel acetylacetonate was charged to a stainless steel bombunder a nitrogen atmosphere. Thereafter, 276 grams of ethylene wereadded to the mixture, and the bomb was closed and heated, accompanied byrocking, to a temperature of 71 C. within a period of 35 minutes. Thepressure within the bomb at this point was 860 p.s.i. Heating wascontinued, accompanied by rocking, at a temperature maintained in therange of from 71 C. to 78 C. for a period of 21 hours, whereupon thepressure within the bomb had dropped to 420 p.s.i. at 75 C. The bomb wasconnected to two Dry Ice traps and vented at room temperature. In thismanner, about 12 grams of benzene, 28 grams of butene, and 4 grams ofbutadiene were removed. The contents of the bomb, together with abenzene rinse, were transferred under a nitrogen atmosphere to adistillation flask. At a reduced pressure of 200 mm. of Hg, 6 grams ofbenzene, 65 grams of butene and 11 grams of butadiene were recovered bydistillation. Similarly, 566 grams of distillate consisting of benzeneand 38 grams of 1,2,3-dimethylenemethyl cyclopentane, as determined bygas chromatography, were obtained upon reduction of the pressure to 3mm. of Hg. Thereafter, a distillate containing 119 grams ofsubstantially pure triethylaluminum was obtained at a temperature in therange of 65 C. to 78 C. under a reduced pressure in the range of 1 to 3mm. of Hg. The 1,2,3 dimethylenemethylcyclopentane-containing distillatewas washed with water and redistilled to yield 23 grames of purifieddimethylenemethylcyclopentane (B.P. 1l8-121 C.), the remainder of thediene being distilled over with benzene. A major fraction of thisproduct, viz. 12 grams, consisting of substantially pure1,2,3-dimethylenemethylcyclopentane, had the following physicalproperties: B.P. 120-121 C., n 1.4621, and d 0.8172.

Analysis.Calculated for C H C, 88.82; H, 11.18; M.W., 108; M (for purel,2,3-dimethylenemethylcyclpentane), 36.02. Found: C, 88.61; H, 11.41;M.W., 108; M 36.40. Based upon molecular refractivity data, andultraviolet and infrared analysis, the product is believed to consist ofapproximately 80 percent 1,3-dimethylene- Z-methylcyclopentane andpercent 1,2-dimethylene-3- methylcyclopentane.

Three milliliters of the 1,2,3-dimethylenemethylcyclopentane product(B.P. 120-121 C.), upon dissolution in 3 ml. of ethanol and the additionof 2 drops of concentrated hydrochloric acid, were hydrogenated overplatinum oxide in a Parr hydrogenator at 40 p.s.i. and room temperaturefor a period of about 1 hour. The pressure was 37.5 p.s.i. at the end ofthis period. The hydrogenated product was washed with water, dried overmagnesium sulfate and anlyzed by gas chromatography, infrared and massspectroscopy. There was thus obtained as products, 1, trans-2,cis-3-trimethylcyclopentane, 1, cis-2, trans-3- trimethylcyclopentane,and 1, cis-2, cis-3-trimethylcyclo pentane in quantitative yield.

Example III In a manner similar to that described above in Example I,1,3-butadiene was reacted with triisobutylaluminum to produce a polymercomprised of a substantial proportion of recurringdi(aluminomethyl)methylcyclopentane units. A mixture of 169 grams ofthis polymer, and 150 grams of benzene was charged to a stainless steelbomb under a nitrogen atomsphere. Thereafter, 373 grams of ethylene wereadded to the mixture, and the bomb was closed and heated, accompanied byrocking, at a temperature maintained in the range of from 82 C. to 86 C.for a period of 21 hours. During this period, the pressure in the bombdropped from an initial high of 1,375 p.s.i. to 1,025 p.s.i. Anethylenically grown polymer composed of a proportion of recurringdi(aluminoalkyl)methylcyclopentane units substantially equal to theproportion of di(aluminomethyl)methylcyclopentane units in the polymericprecursor was formed. The grown polymer was hydrolyzed by reaction withethanol, water, and dilute hydrochloric acid in a manner similar to thatdescribed above in Example I. A two-phase reaction mixture comprising anupper organic layer and a lower aqueous layer was formed. The organiclayer was separated, washed with water, dried over magnesium sulfate anddistilled to yield the following fractions:

Fraction Weight B.P. 0.) Cu range (grams) 3 125-157 Crow 24 157-172 Cw 8172-184.. 010 29 184-214 c C11 23 123/50 mm H /45 mm Cur-C 4 24 142/45mm. Hg.154/10 mm. Hg. Cir-Cm 30 154/10 mm. Hg.-149/l mm. Hg Una-Cm 15149/1 mm. Hg.178l1.4 mm. Hg CnrCzo 0 10 178/l.4 mm. Hg.230/0.7 mm. Hg"(Em-C14 Residue. 7

The fractions were analyzed by gas chromatography. The fractions werefound to be composed of l,2,3-(C C 7, 9, 11', 13, 15, 17 and i yn ypentanes, i.e. cyclopentanes containing three alkyl substituentspossesisng an aggregate sum of 3, 5, 7, 9, 11, 13, 15, 17, and 19 carbonatoms, at least one alkyl radical being a methyl radical, in a totalyield of approximately 70 grams as follows.

Product: Weight, grams Trimethylcyclopentane 8.1 (C -Alkyl)cyclopentane12.0 (c -Alkyhcyclopentane 10.8 (C -Alkyl)cyclopentane 11.4 (C-Alkyl)cyclopentane 14.7 (C -Alkyl)cyclopentane 3.8 (C-Alkyl)cyclopentane 4.9 (c -Alkyncyclopentane 3.1 (C -Alkyl)cyclopentane0.6

Gas chromatographic analysis also indicated the production of acyclichydrocarbons containing an even number of from 8 to 22 carbon atoms in atotal yield of approximately grams. A sample of1,2,3-dimethylpropylcyclopentane obtained from the (C-alkyl)cyclopentanecontaining fraction was further analyzed as follows--Calculated for C H C, 85.63; H, 14.37; M.W., 140.3. Found: C, 85.57; H,14.62; M.W., 140.

A sample of 1,2,3 dimethylpentylcyclopentane obtained from the (O-alkyl)cyclopentane-containing fraction was further analyzed as follows-Calculated for C 'H C, 85.63; H, 14.37; M.W., 168.3. Found: C, 85.20; H,14.35; M.W. 168. Infrared and nuclear magnetic resonance spectra wereconsistent therewith.

Example IV An ethylenically grown polymer, dissolved in benzene, isobtained as described above in Example III. At a 13 containing twow-hydroxyalkyl and one methyl substituent possessing an aggregate sum of3, 5, 7, 9, 11, 13, 17, and 19 carbon atoms, are obtained as products.

Example V In a manner similar to that described above in Example I,1,3-butadiene was reacted with triisobutylalumiuum to produce a polymercomprised of a substantial proportion of recurringdi(aluminomethyl)methylcyclopentane units. A mixture of 172 grams ofthis polymer and 150 grams of benzene was charged to a stainless steelbomb under a nitrogen atmosphere. Thereafter, 369 grams of ethylene wereadded to the mixture, and the bomb was closed and heated, accompanied byrocking, at a temperature maintained in the range of from 85 C. to 90 C.for a period of 48 hours. During this period, the pressure in the bombdropped from an initial high of 1,200 psi. to 830 psi. An ethylenicallygrown" polymer composed of a proportion of recurringdi(aluminoalkyl)methylcyclopentane units substantially equal to theproportion of di- (aluminomethyl)methylcyclopentane units in the polymerprecursor was formed. The bomb was cooled and vented at roomtemperature. To the contents in the bomb, 270 grams of additionalethylene, 17 grams of benzene, and 0.2 grams of nickel acetylacetonatewere added. The bomb was closed and reheated, accompanied by rocking ata temperature of about 68 C. for a period of 19 hours. The pressure,during this period, varied from an initial high of 625 p.s.i. to 525p.s.i. A mixture of dienes and triethylaluminum was thus formed. Theproduct was hydrolyzed by reaction with ethanol, water, and dilutehydrochloric acid in a manner similar to that described above in ExampleI. A two-phase reaction mixture comprising an upper organic layer and alower aqueous layer was formed. The organic layer was separated, washedwith water, dried over magnesium sulfate and distilled to yield thefollowing fractions:

Fraction Weight B.P.( 0.) 0.. range 6 50/200 mm.Hg.-70l200 mm.Hg. Ca 3070/200 mm.Hg.-90/100 mm.Hg Cs-Cm 12 90/100 mm.Hg.-100/100 111.111.Hg..Cs-Cm 19 100/100 mm.Hg.-l20/l00 mm.Hg C 28 120/100 mm.Hg.-l39/50 mm.Hg-010012 34 139/50 mm.Hg.-l34/10 mmJiIg. 012-014 40 134/10 mm.Hg.-132/1.1mmllg 016-018 36 132/11 mm.Hg.-166/1.1 null-H Ora-C20 9 26 166/11mmHg.-186/1.1 mm.Hg C22-C24 Residue. 20

The fractions were analyzed by gas chromatography. There were thusobtained as products 1,2,3-(C C C C C C and C-di[w-alkenyl]methyl)cyclopentanes, i.e. cyclopentanes containing twow-alkenyl and one methyl substituent possessing an aggregate sum of 3,5, 7, 9, 11, 13, 15, and 17 carbon atoms. Gas chromatographic analysisalso indicated the production of emu-alkadienes containing an evennumber of from 8 to 20 carbon atoms. A sample of1,2,3-alkylmethylmethylenecyclopentane obtained from fraction 3 wasfurther analyzed as follows Calculated for C H C, 88.16; H, 11.84; M.W.,136.3. Found: C, 88.43; H, 11.94; M.W., 136.

A sample of 1,2,3-methylmethylenepent-4-enylcyclopentane obtained fromfraction 5 was confirmed in structure by mass and infrared spectroscopy.This product is subsequently converted to 1,2,3-methylmethyleneoxy(4,5-epoxypentyl)cyclopentane by admixing the diene, in ethyl acetate, withan excess over two moles of peracetic acid per mole of diene and heatingthe resulting mixture at a temperature of about 60 C. for several hours.In similar, the other di(w-alkenyl)methylcyclopentanes produced asdescribed above in this example are converted to the correspondingdiepoxides by reaction with excess peracetic acid.

wherein each R, independently, designates an alkyl radical of from 1 to4 carbon atoms, at a temperature of from about C. to about 150 C., in aproportion of isoalkylaluminum to 1,3-butadiene providing an excess overone-third mole of isoalkylaluminum per mole of 1,3-butadiene during thereaction and while removing the isoolefin formed as a by-product fromthe resulting mixture, for a period of time sufficient to produce apolymer composed in substantial proportion of recurring units of theformula:

(b) bringing said polymer into reactive admixture with at least 1.5moles of ethylene per aluminum atom of said polymer, in the absence of acatalyst, at a temperature of from about 80 C. to about 190 C., for aperiod of time suflicient to produce an ethylenically grown polymercomposed in substantial proportion of recurring units of the formula:

H2 Hz 31(CHZCH2) yCH2- -CH2 (CH2CH:) .31

wherein y and z are as defined above; (c) bringing said ethylenicallygrown polymer into reactive admixture with 7 oxygen, at a temperature offrom about 0 C. to about 150 C., for a period of time sufiicient toinsert an oxygen atom between aluminum and adjacent carbon atoms of saidethylenically grown polymer; and (d) hydrolyzing the resultingoxygenated polymer for a period of time sufficient to produce saiddi(w-hydroxyalkyl)methylcyclopentane.

2. A process for the production of adi(w-hydroxyalkyl)methylcyclopentane of the formula:

H2 Hz HOCH2(OH2CH2)y l '(OH:CH2) :CHZOH H H W133 wherein y and zdesignate integers of from 0 to 8, at least one of which is a positiveinteger, which process comprises the steps of (a) bringing 1,3-butadieneinto reactive admixture with an isoalkylaluminum of the formula selectedfrom the group:

A1 CHiC1E\I and HA1 (GHsCH wherein each R, independently, designates analkyl radical of from 1 to 4 carbon atoms, at a temperature of fromabout C. to about C., in a proportion of isoalkylaluminum to1,3-butadiene providing an excess over one-third mole isoalkylaluminumper mole of 1,3-

15 butadiene during the reaction, and while removing the isoolefinformed as a by-product from the resulting mixture, for a period of timesutficient to produce a polymer composed in substantial proportion ofrecurring units of the formula:

(b) bringing said polymer into reactive admixture with at least 1.5moles of ethylene per aluminum atom of said polymer, in the absence of acatalyst, at a temperature of from about 85 C. to about 120 C., for aperiod of time sufficient to produce an ethylenically grown polymercomposed in substantial proportion of recurring units of the formula:

Hz'-Hz BKCHQCHD CH2- CH(CHH;C) ,al H H Wm wherein y and z are as definedabove; (0) bringing said ethylenically grown polymer into reactiveadmixture with oxygen, at a temperature of from about 30 C. to about 60C., for a period of time sufficient to insert an oxygen atom betweenaluminum and adjacent carbon atoms of said ethylenically grown polymer;and (d) hydrolyzing the resulting oxygenated polymer for a period oftime sufiicient to produce said di(w-hydroxyalyl)methylcyclopentane.

3. The process according to claim 2 wherein said triisoalkylaluminum istriisobutylaluminum.

References Cited UNITED STATES PATENTS 6/ 1964 DAlelio 260-448 5/ 1962Johnson et al. 260-448

